Vapor-Phase Infrared Spectral Study of Analogs of the Nerve Agent Sarin

McGarvey, David J.; Stuff, John R.; Williams, Barry R.; Durst, H. D.

doi:10.1080/00387010009350158

Cited by 12 publications

(13 citation statements)

References 7 publications

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“…2. In OPs these different IR adsorptions are dependent on the identity of the ligands attached to the phosphate and can be used to distinguish between G and V agents as well as Sarin analogs and precursors [31,32].…”

Section: Resultsmentioning

confidence: 99%

Infrared signature of micro-hydration in the organophosphate Sarin: an ab initio study

Alam

Pearce

2015

J Mol Model

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The infrared (IR) spectra of micro-hydrated Sarin•(H2O)n clusters containing between one and four explicit waters have been studied using ab initio density functional theory (DFT) methods. The phosphate group P=O bond vibration region (∼1270 to 1290 cm(-1)) revealed the largest frequency variation with hydration, with a frequency red shift reflecting the direct hydrogen bond formation between the P=O of Sarin and water. Small variations to the P-F stretch (∼810 to 815 cm(-1)) and the C-O-P vibrational modes (∼995 to 1004 cm(-1)) showed that the water interactions with these functional groups were minor, and that the structures of Sarin were not extensively perturbed in the hydrated complexes. Increasing the number of explicit hydration waters produced only small vibrational changes in the lowest free energy complexes. These minor changes were consistent with a single water-phosphate hydrogen bond being the dominant structure, though a second water-phosphate hydrogen bond was observed in some complexes and was identified by an additional red shift of the P=O bond vibration. The H2O•H2O vibrational modes (∼3450 to 3660 cm(-1)) increased in complexity with higher hydration levels and reflect the extended hydrogen bonding networks formed between the explicit waters in the hydrated Sarin clusters. Graphical Abstract Ab initio studies of the infrared signature for micro-hydrated Sarin.

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Section: Resultsmentioning

confidence: 99%

Infrared signature of micro-hydration in the organophosphate Sarin: an ab initio study

Alam

Pearce

2015

J Mol Model

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“…If these values hold true for vapour phase spectra then P-propyl isomers should be differentiated. In two recent studies [10,11], involving analogues of the nerve agent sarin and dialkyl alkylphosphonates respectively, P=O stretching frequencies were compared for a range of methyl-, ethyl-, isopropyl-and n-propyl-phosphonyl compounds. McGarvey et al [10] obtained data from methyl-, ethyl-and n-propyl compounds, and a limited number (four) of dialkyl isopropylphosphonates.…”

Section: The P=o Groupmentioning

confidence: 99%

“…In two recent studies [10,11], involving analogues of the nerve agent sarin and dialkyl alkylphosphonates respectively, P=O stretching frequencies were compared for a range of methyl-, ethyl-, isopropyl-and n-propyl-phosphonyl compounds. McGarvey et al [10] obtained data from methyl-, ethyl-and n-propyl compounds, and a limited number (four) of dialkyl isopropylphosphonates. The only significant difference observed was in the P=O stretching frequency at 1251 cm −1 for P-isopropyl-, contrasting with 1261-1268 cm −1 for the other compounds studied.…”

Section: The P=o Groupmentioning

confidence: 99%

Identification of iso- and n-propylphosphonates using liquid chromatography–tandem mass spectrometry and gas chromatography–Fourier transform infrared spectroscopy

Cooper

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Timperley

et al. 2004

Journal of Chromatography A

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“…Since nerve agents are rather volatile compounds with sufficient thermal stability, and, in addition, contain a phosphorus (P) atom, gas chromatography-mass spectrometry (GC-MS), 1 GC with ame photometric detection (FPD) or GC with nitrogenphosphorus detection (NPD) are very suitable combinations for selective nerve agent detection and quantication 4 and play a major role nowadays. The other techniques include ame ionization detection (FID), 5 photoionization detection (PID), 6 ion mobility spectrometry (IMS), 12 Fourier transform infrared spectroscopy (FTIR), [7][8][9] semiconducting sensors, 10,11 and direct air-sampling mass spectrometry. [13][14][15][16][17][18] However, some of these techniques have their individual limitations for nerve agent detection.…”

Section: Introductionmentioning

confidence: 99%